FR2537150A1 - RECORDING LIQUID - Google Patents

Abstract

THE INVENTION RELATES TO A RECORDING LIQUID. THE LIQUID OF THE INVENTION CONSISTS OF A COLORING MATTER AND ITS LIQUID MEDIUM OF DISSOLUTION OR DISPERSION, THIS LIQUID CONTAINING AT LEAST ONE OF THE COLORANTS REPRESENTED BY THE FORMULA: (CF DRAWING IN BOPI) IN WHICH R IS AN ORGANIC RADICAL AND M IS A CATION CHOSEN BETWEEN NA, K, LI, NH AND AN AMINE SALT. APPLICATION TO AN INKJET RECORDING SYSTEM.

Description

The present invention relates to a new recording liquid and it

  focuses in particular on a new recording liquid that can be used in a recording system that involves the ejection of droplets of the recording liquid through ends.

  ducts (discharge ports) starting from a registered head

  manager to complete the recording.

  For recording on media such as paper and similar media using writing instruments (pen holder, felt pen, etc.), so far, inks which are solutions of various dyes in the water or

in an organic solvent.

  It is also known that recording liquids

  similar compositions are used in the recording systems mentioned above, referred to

  ink jet, in which the ejection of the recording liquids

  The recording is carried out by vibration of piezoelectric oscillators, by electrostatic attraction due to the application of a high voltage or by some other action. However, the recording liquids for the ink-jet recording system must satisfy to more rigorous performance characteristics,

  compared to recording liquids for instru-

  Writing instruments such as pen holder and pencil

felt.

  There are various types of ink jet recording systems that differ in the methods by which the recording liquid droplets are generated.

  and the flight directions of the droplets are set.

  An example is given in Figure 1 of the accompanying drawings The device of Figure 1 is a recording unit which generates droplets of recording liquid in response to signals applied to a piezoelectric oscillator integral with a head

  In FIG. 1, 1 denotes the registered head.

  controller equipped with a piezoelectric oscillator 2a, a vibrating plate 2b, an intake duct 3 for the recording liquid, a chamber 4 containing the

  liquid and a discharge port 5 The recording liquid

  7 is introduced into the liquid chamber 4

  from a reservoir 6 via a supply line 8.

  An intermediate treatment unit 9 such as a pump or a filter is provided, if necessary, in the middle of the feed pipe 8 Recording signals converted into pulsed signals by means of a signal processing member 10 (for example a generating organ

  pulses) are applied to the piezo oscillator

  2 to vary the pressure of the recording liquid in the liquid chamber 4 in accordance with the applied signals. As a result, the recording liquid 7 is discharged in the form of droplets 11 through the orifice 5 to form a fluid. recording at

  the surface of a suitable medium 12.

  Various types of devices are known, besides the one described above; for example, there is known a variant of the device of Figure 1 which comprises, as shown in Figure 2, a liquid chamber

  4 in the form of a nozzle, surrounded by a piezo oscillator

  The droplet production mechanism in this device is basically the same as in the device of FIG. 1 In accordance with another known device, droplets of electrically charged recording liquid are produced continuously and parts of the droplets are In another known device, thermal energy corresponding to the recording signals is applied to the recording liquid in the recording head to produce droplets.

recording liquid.

  An example of the thermal energy device is shown in Figs. 3A, 3B and 4. Fig. 3A is a cross-sectional view of a recording head 13 in the direction of the ink jet and Fig. 3B is the cross-sectional view along the line AB of FIG. 3A. The recording head 13 is made by connecting a glass, ceramic or plastic plate with a channel 14 for passing the ink with a heating head 15 for heat-sensitive recording (it is shown as thin films in the figures, but it is not limited to such a shape)

  for communicating thermal energy to the ink.

  The heating head comprises a protective film 16 made, for example, of silicon oxide; aluminum electrodes 17-1 and 17-2; a layer 18 forming a heating resistor, for example nickel-chromium; a layer 19 accumulating heat; and a substrate 20 made, for example, of alumina having a good release property

heat.

  The ink 21 is loaded into the channel 14 to its discharge port 22 and forms a meniscus by the action of the pressure P. When an electrical signal is applied to the electrodes 17-1 and 17- 2, the region represented by N of the heating head 15 generates quickly the

  heat, bubbles are formed in the ink 21 as

  tact of the region n, the meniscus of the ink is projected-

  by the action of the resulting pressure and an ink droplet 24 is discharged through the orifice 22 and is projected towards a recording medium 25 FIG. 4 shows the appearance of a multiple head which comprises rhe

  row of heads as shown in Figure 1.

  The multiple head is made by bonding a glass plate 27 having several channels 26 with a heating head 28 similar to that shown in Figure 3 A.

  The recording liquid used for the

  Ink-jet recording is basically composed of a coloring matter (a dye or pigments) and a liquid medium (water, various organic solvents and their mixtures may be used) for its dissolution or dispersion and, where appropriate, it contains certain additives. Such recording liquids have been described, for example, in Japanese Patent Publication Nos. 8361/1975, 40484/1976, 13126/1977 and 13127/1977 and in US Pat. Japanese put on inspection

  under the number 95008/1975.

  For the ink jet recording liquid, the required performance characteristics are more stringent than for a general type ink used for writing. These required performance characteristics are as follows:

  (1) The physical properties of the recording liquid

  such as viscosity, super-

  and the electrical conductivity must satisfy

  the discharge conditions (eg the voltage

  the piezoelectric element and the frequency; the

  dimensions and the shape of the orifice and the material

both this orifice) -

  (2) It is stable during long storage

  term without causing closure of the orifice.

  (3) It is fixed quickly on recording media such as paper, film, etc., the contours of the resulting ink dots are sharp and the absorption

  ink forming the points is minimized.

  (4) The color of the resulting image is clear

and dense.

  (5) The resulting image is excellent in

  its wet strength and its solidity to light.

  (6) It does not attack any of the materials (its reci-

  the communication tubes, the seals,

etc.) to his touch.

  (7) It has no unpleasant odor, toxicity, flammability, etc. It is very difficult for the recording liquid to present the indicated characteristics at the same time.

  above The above-mentioned recording liquids, belonging to

  keeping with the prior art, do not give satisfaction to

this point of view.

  The characteristics of the recording liquid depend to a large extent on the properties of the dyestuff, since the recording liquid is basically composed of a dyestuff and its dissolution or dispersion medium, as shown in FIG. As a result, it is very important in practice to choose the dyestuff so as to provide the recording liquid with the required characteristics.

indicated above.

  One of the aims of the present invention is to propose a new mono-azo compound which can be

  used as a coloring matter of a recording liquid

  which satisfies, at the same time, the requirements (1) to (7)

  mentioned above with regard to the characteristics

performance.

  In accordance with one aspect of the present invention,

  tion, it is proposed a registration fee comprising a coloring material, which is a training component

  image, and a liquid dissolution or dispersion medium

  of the coloring matter, said recording liquid

  being characterized in that it contains, as a component

  image formation, at least one of the dyes represented

  with the following general formula (A):

Q 1 N = N Q 2 _ N = N Q

  wherein Q 1 and Q 3 each represents a substituted phenyl or naphthyl group bearing at least one SO 3 M substituent and Q 2 represents a substituted naphthyl group bearing at least one SO 3 M substituent, M being a selected base between

  the Na, K, Li, NH 4 cations and the cations of an amine salt.

  According to another aspect of the invention there is provided a recording liquid comprising a coloring material, which is an imaging component, and a liquid medium for dissolving or dispersing the coloring material, said recording liquid being characterized in that it contains as imaging component at least one of the dyes represented by the following general formula (B): OH

MO 3 S> \ Q N = N 0 / N = N NHR

o 3 3 'd O 3 S / / 503 M

SO 3 M

  where R is a representative of the group including the remains

', R 3 R 6

  At-CO-p 9 O R 1 R 2 R R 5 OHR I and -w N =

8

R 72 R 5 6 7 8 9

  R 1, R 2, R 3, R 4, R 5, R 6, R 8 and R 8 being each a repre-

  having the group comprising H, CH 3, C 2 H 5, C 1, NH 2, OH and OCH 3; and M represents a base selected from Na, K, Li,

  NH 4 and amine salt cations.

  In the accompanying drawings: Figures 1 and 2 are schematic representations of ink jet recorders; Figs. 3A and 3B are respectively vertical and cross-sectional views of the head of another ink jet recorder; and Fig. 4 is a perspective view of a multiple head which is formed of a row of heads as shown in Figs. 3A and 3B. Representative dyes of formula (A) according to the present invention. are the following: Na SO SO 3, Na NH 2 SO 3 Na

(2) Q - N = N- <5> -N = N (

SO 3 Na NH 2

OH NH 2

(3) N = N -N- (

  ## STR2 ## ## STR1 ##

011 NH>

  Na 3 S N = N 0 = N (ro 503 Na 503 Na)

(7) Na O 3 S = N N = N -

-SQ Na

2537 150

  OH (8) Nao 3 S N = N N = N-, cQ Nao 3 S N 112 SQ, Na (9) S Na Na, Na (10) Li QS, (11) OH

NIICOCI-13

  SO ,, t Na (12) Nao's O-, Ni OH (13) Na SO Co

N = N O 1 \, - N = N 00

  Na QS 503 Na (Na Na, Na (14) Na Oa S N = N N = N 503 Na Na

(15) = N N =

503 Na 803 Na 503 Na

NH NH 2

N = N N = N O

503 Na S O, NaSO Na OH

(17) N = N N = N

  Na 3 S SO Na 503 Na 1 (18) (19) 1 HO 503 Na (20) (21)

OH OCH 3 -

(22) Na O 3 S N = N N = N -

Na 3 O 3 Na Na Na

253715-0

  S10H (LZ) (9 z) if (SZ) (.PZ) c (EZ) y m HN OS. & Issa at 1 o OH-

(28)

OH (29) Nia Ozi

CH 2 CH 2 OH

R = HNKCH 2 CH 2 OH

CH CH OH

  2 2 (30) SO 3 Na SO 3 Na SO Na 1 4 OH

H IN YH

N = N O O -N = N

R 035

R 038 503 R

CH CH OH

2 2 o R = HNH 2 CH 2 OH

H CH OH

2 2

9.H QH

  (32) Na O 3 = N N = N 503 Na SO 3 Na (33) CNCOs

N = N 'N (SE)

= N- (D-scot

úI-IDODHN OH

  eeos 81: OLINT = N = 1400-scoem ao HO geos

HOOOHN OH

  The eos The e Os M = N HO> our> fos sú O X) -Fn, HM N - \, o M N O oseicsz

253? 150

  1 6 503 K (39) H 3 C - (C) -N = 1503 K 503 K HO (40) 503 Na

-NHCO-OD

503 Na Na O 3 HO

(41)

(42) -

S 03 Na OH NH 2 -

(43) 02 N = N

  O 3 S 503 Na S 3 to 1 7 OH N Hz (44) 503 Na 3 Na

(45) H 3 C

503 Na 503 Na NH 2

--N = N N

at S 503 Na 503 Na

NHCOCH 3

-00 = N = N N = N

  Na (35) (NaCl) (47) NaH (48) Na 2 O 3 S D N = N 503 Na 2 SO 4. , Na 503 Na, OH

(50) "N = N

0 Y N = N

  NaNO (50) Na (51) 503 NaHCO3 Na (52) Na2O 3 S = N Na 503 Na 503 Na

503 Nà

(53) NaOs / Nz = N-, f

PI 50

  1 8 (49) Na O 3 S O W N, \ ONN- / '7 \\

01 jo -

  SO, 3 Na SCOEN (ZS) oz if (99) HO Nz H z H z H Oz H Dz H H = 8 -1 O HO ZH Dz H sgou (99) I 70 exco s 6 L

OS & IESZ

  (58) Na 3 Na 3 O 3 S (59) Na 3 S Na Na 3 O 3 Na 3 O (60) Li 3 S 5 Li 3

01-1 OH

(61) N 403 -N-N-e-SO 3 Na

03 Na -

(fl?) 503 Na

ONE, (S

N = N S ú OUN (99)

-CO> CO-

N (C-9)

  z z HD H Oz HD z H H = Ë H Oz HZ) z H i O l úou (9)? Neos? NúOS

N = N-Q

HO S COM (ú 9)

j CI

& ZúSZ

  s: ORN (11) (OE) (69) UN (29) (z 9) e Neos LINCO

-N SOON

Nco Ho osiúSZ

N S C O 'ON')

-e-. (SL) if úOe N (U) (M) e Neos

COUN (ZL)

OH oseiúsz NHCO-e

(77) K 03

i) (78) SO Na (79) Na Oi

(80).

(81)

03 Na HO Na O, 0., Na

HO NHCO

1 1 00

(82) / OH 7 i-11 Ce, SOaLi (84)

S (3 NI 14

i 5 (85) R

CH CH OH

o R = HN CH 2 CH 2 OH

CH 2 CH 2 OH -,

2.5 (83) Li HO (86)

3 NITL-

  (87) Naffl-N MH HO NH DOE, Na 3 -503 Na 2 Na 3 Na (8 s) Na 3 O 3, 503 Na

HO NHCO- 5

(89) KOS-p-N =

K 03 503 K

  SO ,, K (90) Na 0 35 503 Na 7 D e OR N (95) OH (f 6)

HN OH

  Scoe N (95) OH s COVN scolo N OH UNCOS UNIOS S'Oe N Sc Ot N (T 6) s Hz OH LZ 253 ilso CH 3 (96) Li (3 IC 503 Li 3 Li (97)) y Na O -3 S

SO., Na -

503 Na (98) NaO 3 (99) NaO 3

(100) FLN 03-, ç

S (3 Na

503 Na -

503 Na SO Nlit

03 NFI,

HO NH 2

  (101) Na O 3 SQ -N Q N O Na O 3 S SO 3 Na SO 3, Na

H 10C (

  Examples of dyes of formula (B) according to the present invention include the following:

(103)

HO SO Na,

(104) H

  Na OS - N = N Q-N == N -NH O O Na SO 503 Na SO 3 Na 3 O HO

(105)

  Na 0, SO Na = SO ,, Na HO 1, N = Nf CoNff W e ce Na O -is SO Na, Na

HO N ç OH

N = N NH- 1 Y

N- This Na 3 S 503 Na 803 Na

(10 6)

Na QS D-N = N-

(107)

(108)

  HO Li O 3 S-N = N -N = N NHCO-D LiO 3 03 Li SO Li

(109)

Li 03 S - "DN = N.

HO

N, <OH

m N == \ This S Oli z z

HO HD HD

  ## STR1 ## where:

HO HD HD

* HO H; HD D H = s lo

HO HD H

O l REFLECTIONS UUOS SE O,

_ODHN '' N = N

OH

(111)

the Heos SúONI

- (D-OD N-

N = N-CO:> - SúONi OH

(011)

O 5-e i eeos

W-D "DIHN

(LTI) HWOS

(9-ET)

if

5-WHN

c Ha - HN OH

(E 11)

oseigsa

253 7,150

(1 18)

  HO Na O 3 S - 5-N = N NHe 03 Na Oa Na

(1-19)

(120)

  Na 2 O 3 Na 2 O 3 S O 3 N O Na Na

(121)

  HO NHCO-Ce% Ce 503 Na Na O 3 S-D-N = N 503 Na

(1 22) HO CH

  Lio 3 S N = N -N N NHCO- -H 2 The 03 503 Li 03 L i

(123)

HO

NHCO-, 5 -OCH,

Na 3 S -N = N NaE 33 803 Na 503 Na

(124)

  CH 3 H 2 O Na OS fnH Na (3 O Na 03 Na

(125) HO

  Na 3 S00-N = N -N = N NHSO NH 2 Na 3 O 3 S 503 Na 3 Na

(126)

c T HO i NH 502-e-I \ IH 2

HIN 035

HNO

503 r 4

O., NH 4

  127) HO Na O 3 S <> = N -N = N X NHCO CH 3 Na 3 SO 3 Na SO 3 Na

C 128)

HO

H 4 NNO S N = N NHCOCH 3

SO 3 NH 4

  According to the present invention,

  obtain a recording liquid that has

  physical properties such as viscosity and super-

  within the limits of the respective correct ranges and a high speed of fixing; which does not cause the plugging of an orifice of very small diameter; none of the physical properties of which vary or do not form a precipitate of solid material during storage; which can be applied to various recording media without any particular restriction; and which forms very dense images endowed with a very good solidity with the water, the light and the friction and of a high degree

resolution.

  The content of the recording liquid in the mono-azo compound, i.e. the dye of the present invention, is selected according to the types of components of the liquid medium and the characteristics that the recording liquid must have, but it is generally between 0.1 and 20%, preferably between 0.5 and% and especially between 1 and 10% by weight on the basis of

  total weight of the recording liquid The recording liquid

  The registration of the present invention may contain one or more of these monoazo dyes as essential components in the presence or absence of any of various other dyes such as direct dyes.

and acid dyes.

  Water alone or in admixture with a water-miscible organic solvent can be used as the liquid medium of the recording liquid of the invention. Examples of the water-miscible organic solvents are C 1 to C alcohols. 4 such as methanol, ethanol,

  n-propanol, isopropanol, n-butanol, sec -

  butanol, tertiary butanol and isobutanol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone

  and diacetone alcohol; ethers such as tetra-

  hydrofuran and dioxane; nitrogen-containing heterocyclic ketones such as N-methyl-2-pyrrolidone

  and 1,3-dimethyl-2-imidazolidinone; polyalkylene

  glycols such as polyethylene glycol and polypropylene

  glycol; C 2 to C 6 alkylene glycols such as ethylene

  glycol, propylene glycol, butylene glycol, trihydric

  ethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol; 1,2,6-hexanetriol; glycerol;

  and lower alkyl ethers of polyhydroxy alcohols

  such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether and

  the monomethyl (or mono-ethyl) ether of triethylene

  glycol. The content of the recording liquid in a water-miscible organic solvent is in general from 5 to 95%, preferably from 10 to 80% and in particular from 20 to 50% by weight.

  based on the total weight of the recording liquid.

  The water content of this liquid is chosen in a wide range according to the types of components of the medium

  the composition of this medium and the characteristics

  the recording liquid, but it is generally from 10 to 90%, preferably from 10 to 70% and in particular from 20 to 70% by weight on the basis of the weight

total of the recording liquid.

  The recording liquid of the present invention prepared from the above components is in itself superior and well balanced with respect to the recording performance characteristics (signal response capability, droplet production stability, Discharge stability, continuous working capacity for long hours and stability

  after a long rest), the stability at

  posage, the ability to attach to recordings

  However, various known additives can also be incorporated into the recording liquid. The light fastness, the resistance to atmospheric factors and the wet fastness of the resulting image.

  above to further improve these characteristics.

  Such additives include, for example, viscosity modifiers such as a vinyl alcohol polymer, cellulosic resins and other water-soluble resins; various types of cationic, anionic and nonionic surfactants; voltage modifiers

  such as diethanolamine and triethanolamine

  amine; p-influencing substances such as buffer solutions; and Fungicides For the preparation of a recording liquid for use in the recording system of the ink jet type based on the electric charge of the recording liquid, it is

  adds as resistivity modifier an inorganic salt

  that such as lithium chloride, ammonium chloride

or sodium chloride.

  When the recording liquid is used in the recording system of the ink jet type based on the action of thermal energy, the thermal properties can sometimes be conditioned (for example the specific heat, the coefficient of expansion thermal

  and the thermal conductivity) of the recording liquid.

  Other details of the present invention

examples

Example 1

  A recording liquid was prepared by intimately mixing the following components, filtering the resulting solution under pressure through a 1-pore "Teflon" filter and degassing the filtrate under vacuum. Composition Color (dye NO 23 of the above list) 3 parts Diethylene glycol N-methyl-2-pyrrolidone Water 52 The resulting recording liquid was subjected to the following tests T 1 T 5 using a d recording of the ink jet type operating at the

  demand, which discharges droplets of liquid

  by means of piezoelectric oscillators (diameter of the orifice 50 Fm, control voltage of the

  60 V piezoelectric oscillators, 4 kHz frequency).

  The results of all the tests were satisfactory.

  (T 1) long-term storage stability of the recording liquid: After the sample has been placed in

  clogged glass containers and that it has been stored

  6 months at -30 ° C or 60 ° C, no deposit of insoluble matter was observed and no change in physical properties or color changes was observed.

found in the sample.

  (T 2) Discharge stability The sample was continuously discharged for 24 hours at room temperature, at 50 ° C or at C, and as a result, good quality recordings were consistently obtained throughout

  the test period at all temperatures.

  (T 3) discharge response capacity The sample was discharged intermittently at 2-second intervals and discharged after a 2-month rest period. In both cases, a record was obtained.

  stable and uniform without obturation of the orifice.

  (T 4) quality of formed images: Images formed using the sample had a high optical density and were sharp and clear These images, exposed to ambient light in a room for 3 months showed only a loss of optical density equal to or less than 1% Immersion

  in water for 1 minute sheets of paper

  both recordings produced only a very small

smearing images.

  (T 5) ability to attach to various types of recording paper:

  Images formed by using the sample

  the following types of paper were rubbed with the finger for 15 seconds after the recording and the shifting and smearing of the rubbed portions of the images were inspected. The results indicated that there was no displacement or smearing, what is the

  evidence of a good fixing capacity of the recording liquid

tration.

Example 2

  We prepared in the same way as in the example

  1, a recording liquid of the following composition.

  Trade Name Quality or pap 'Manufacturer of Paper Type Paper Manufacturer Ginkan High Quality Sanyo Kokusaku Pulp Co., Ltd. Seven High Quality Hokuetsu Seishi Star Co, Ltd. Haku-botan Quality Honshu Seishi Medium Co, Ltd. Type Unsealed Paper Toyo Roshi Co, Toyo Filter Ltd. N 4 Composition: Colorant (N 36 dye of the above list) 3 parts Diethylene glycol 20 "N-methyl-2-pyrrolidone 20" Water 57 "This recording liquid was subjected to T 1 T 5 tests of the same way as in Example 1, but using a multiple recording head of the

  inkjet type running on demand, which discharges.

  droplets of recording liquid by the action

  thermal energy (orifice diameter 35 Dm, resistance

  heating power 150 Q, working voltage 30 V,

  frequency 2 kHz) All results were satisfactory.

Example 3

  By proceeding as in Example 1, a recording liquid of the following composition was prepared and subjected to the tests.

  T 1 T 5, but using a multiple recording head

  Ink-jet type operating on demand

  (the same as that used in Example 2).

  All results were satisfactory.

  Composition: Colorant (N 44 dye of the above list) 2.5 parts Diethylene glycol 20 N-methyl-2-pyrrolidone 15 "Polyethylene glycol (300 molecular weight) 10" Water 52.5

Example 4

  Proceed as indicated in the example

  1, a recording liquid of

  next position that was tested T 1 T 5, but using a demand-driven inkjet type multiple recording head (same as used in Example 2) All

results were satisfactory.

  Composition Colorant (dye No. 77 on the list above) 3 parts Diethylene glycol 20 N-methyl-2-pyrrolidone Water 57

Example 5

  Proceed as indicated in the example

  In FIG. 1, a recording liquid of the following composition was prepared and tested at T 1 T 5, but using an inkjet-type recording multiple head operating on demand (FIG. even that

  the one used in Example 2). All the results

States have been satisfactory.

  Composition Color (dye No. 67 in the above list) 2.5 parts Diethylene glycol N-methyl-2-pyrrolidone Water 62.5

Example 6

  Proceed as indicated in the example

  Fig. 1, a recording liquid of the following composition was prepared and tested at T 1 T 5 using a jet type recording head.

  ink on demand (with piezo oscillators)

  Electrical type of the type used in Example 1) All results were satisfactory.

  Composition: Colorant (No. 103 dye of the above list) 3 parts Diethylene glycol N-methyl-2-pyrrolidone Water 52

Example 7

  By proceeding as in Example 1, a composition recording liquid was prepared.

  following test and was tested at T 1 T 5, but in use

  reading a recording-type inkjet-type multiple recording head (the same as that used in Example 2) All results were

been satisfactory.

  Composition: Colorant (dye No. 107 on the list above) 2.5 parts Diethylene glycol 25 "N-methyl-2-pyrrolidone 20" Water 52.5 "

Example 8

  Proceed as indicated in the example

  1, a composition recording liquid was prepared.

  Next, it was subjected to T 1 T 5 tests, but using a demand-driven inkjet type multiple recording head (the same as that used in Example 2). All results

have been satisfactory.

  Composition: Colorant (dye N 104 from the above list) 2.5 parts Diethylene glycol 20 "N-ethyl-2-pyrrolidone 15" Polyethylene glycol (molecular weight 300) 10 "Water 52.5"

Example 9

  By following the steps in the example

  1, a recording liquid of the composition

  Next, it was subjected to T 1 tests T 5, but using a demand-driven ink jet type multiple recording head (the same as that used in Example 2). All results have

been satisfactory.

  Composition: Colorant (dye N 116 from the above list) 3 parts Diethylene glycol 20 "N-methyl-2-pyrrolidone 20" Water 57

Example 10

  By following the steps in the example

  1, a recording liquid of the composition

  Next, it was subjected to tests T 1 T 5, but using an ink-jet type multiple recording head operating on demand (the same as that used in Example 2). ) All results have

been satisfactory.

  Composition: Colorant (dye N 111 from the list above) 3 parts Diethylene glycol 20 "N-methyl-2-pyrrolidone 15" Water 62 "

Example 11

  A recording liquid of the following composition was prepared in the same manner as in Example 1. Composition: Colorant (N 90% dye of the above) 4 parts Diethylene glycol 25 "N-methyl-2-pyrrolidone Water 51 A marker was filled with this recording liquid and write tests were performed on medium-grade paper (trademark: Haku-botan, from Honshu Seishi Co., Ltd.) to examine the wetness of the writing images and the writing ability after pencil rest for 24 hours, the cap being removed The results indicated that the recording liquid was of very good quality both in wet strength and in writing ability

after rest.

Example 12

  A recording liquid of the following composition was prepared in the same manner as in Example 1. Composition Colorant (dye No. 128 of the above list) 4 parts Diethylene glycol N-methyl-2-pyrrolidone Water 51 This recording liquid, -supplied to the same tests as in Example 11, has proved very advantageous.

  both in its wet strength and the ability to write

after rest.

Examples 13-79

  The recording liquids of the compositions indicated in the following table were prepared in the same manner as in Example 1 and were subjected to T T tests. On the table, the numbers in parentheses indicate the respective proportions (parts).

by weight) components.

  All of these recording liquids have been shown to be very beneficial in terms of long-term storage stability, recording characteristics (discharge stability, discharge response capacity, etc.), fastening ability, and clarity of the recording media. recorded images, etc.

BOARD

  EXAMPLE NO. Copstodumelium 13 (3) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidone (15) 14 2 (3) Water (62), diethylene glycol ( 30), N-methyl-2-pyrrolidone (5) 5 (2) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 16 3 (2) Water (58), diethylene glycol (30), monomethyl ether of triethylene glycol (10) 17 7 (2.5) Water (52.5%), diethylene glycol (20), N-methyl-2-pyrrolidone (15%), polyethylene glycol (PM 200) (10) 18 11 (3) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidohe (15) 19 12 (2) Water (58), diethylene glycol ( 30), N-methyl-2-pyrrolidone (10) 14 (3) Water (62), diethylene glycol (30), N-methyl-2-pyrrolidone (5) 21 (2) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 22 16 (3) Water (62), diethylene glycol, (20), N-methyl-2-pyrrolidone (15) 23 19 (2) Water (58), diethylene glycol (30>, N-methyl-2-pyrrolidone (10) 24 (3) Water (62), ethylene glycol (25), 1,3-dimethyl-2-imidazolidinone (10) 22 (3) Water (62), ethylene glycol (30), polyethylene glycol (PM 200) (5) 26 18 (2) Water (53>, diethylene glycol (30), N-methyl-2-pyrrolidone (15) 27 (3) Water (62), ethylene glycol (25), 1,3-dimethyl-2-imidazolidinone (10) ) Copstodumyl number of example dye Copsto dumleliie 28 f 21 (3) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidone (15) 29 24 (3) Water (62), diethylene -glycol (20), (2) N-methyl-2-pyrrolidone (15) 30252 Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 31 26 (3) Water (62) ), ethylene glycol (25), 1,3-dimethyl-2-imidazolidinone

<* 10)

  32 27 (3) do 33 29 (3) Water (62), Ethylene Glycol (30), Polyethylene Glycol (PM 200) (5) 34 (3) to 35 (3) Water (62), Diethylene Glycol (20), N-methyl-2-pyrrolidone (15) 36 (2) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 37 41 (2) d 38 j 43 (2) ) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 39 47 (2) d 48 (2> d O 41 52 (3) Water (62), diethylene glycol (20) N-methyl-2-pyrroli: done (15) 42 (3) Water (62), ethylene glycol (25), 1,3-dimethyl-2-imidazolidinone (10) 43 57 (3) Water (62) ), - ethylene glycol (30), polyethylene glycol (PM200) (5) 44 60 (3) d 63 (2) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidene ( ## EQU1 ## Example of a thermoplastic dye 46 66 (2) Water (58), diethylene-g 2 -ocoi (30),

N-methyl-2-pyrrolidone (10).

  (3) Water (62), ethylene glycol (25 d), 1,3-dimethyl-2-imidazolidinone (10) 48 70 (3) d 49 72 (3) Water (62), ethylene glycol (30), polyethylene glycol (MW 200) (5) 73 (2-) Water (58), dimethylene glycol (30), N-methyl-2-pyrrolidone (10) 51 74 (2) do 52 75 (2) do

53 76 (2)

  (3) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidone (15) 79 (2) Water (58), diethylene glycol (30), N-methyl-2 pyrrolidone (10) 56 82 (3) Water (62), ethylene glycol (25), 1,3-dimethyl-2-imidazol idinone (10) 57 84 (3) d 58 85 (3> do 59 88 (3) ) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidone (15> 91 (2) Water (58), diethylene glycol (30), N-methyl-2-pyrrolidone (10) 61 94 (2) do 62 97 (2) do 63 101 (3) Water (62), diethylene glycol (20), N-methyl-2-pyrrolidone (15) 64 102 (3) No. Copolymer example dye 105 (3> Water (62), diethylene glycol (30), N-methyl-2-pyrrolidone (5) 66 (3) Water (62), ethylene glycol (30), polyethylene- glycol (PM 200) (5)

  67 108 (3> Water (62), diethylene glycol (20>, -

  N-Methyl-2-pyrrolidone (15) 68 109 (2 to 5) Water (52.5), diethylene glycol (20), N-methyl-2-pyrrolidone (15), polyethylene glycol (MW 4,200) (10> 69 111 O (2) Water (58%), diethylene glycol (30%),

Monomonomethyl ether of triethyl

  ethylene glycol (10) 112 (3) Water (62), ethylene glycol 25), 1,3-dimethyl-2-imnidazolidinone (10) 71 113 (2) water (53), diethylene glycol (30), N 2-pyrrolidone (15) 72 114 <2) d 73 116 <3) Water (52), diethylene glycol (30), N-methyl-2-pyrrolidone (15) 74 118 (2) Water (58), diethylene glycol ( 30),

monomethyl ether of triethyl

  ethylene glycol (10) 119 (2.5> water (52.5), diethylene glycol (20), N-methyl-2-pyrrolidone (15), polyethylene glycol (MW 200 YOP) 76 120 (3) water ( 62>, diethyleneglycol (20), 1,3-dimethyl-2-imidazolidinone 77 122 (3) Water (64), ehln-lc 13 78 1223 () Water (64) -, ethylene glycol (30) , 79 127 (2) Water (53), diethylene glycol (30), N-methyl-2-pyrrolidone (15)

253715 O

  As illustrated above, the recording liquid

  of the invention offers the following advantages: (1) It has good storage stability at

  long term, barely closing the discharge port.

  (2) It can be stably discharged within a wide range of variations with respect to

  concerns the temperature and working conditions.

  (3) It is quickly set in the middle of

  recording and gives clear and sharp images

  (4) Images printed with this liquid pre-

  feel good with water and light.

  (5) It is very safe and does not attack any material that may come into contact with it, for example its container, seals, etc.

Claims (4)

  A recording liquid comprising a coloring material which is an image-forming component and a liquid medium for the dissolution or dispersion of the coloring material, characterized in that it contains as an image-forming component at least 1 one of the dyes represented by the following general formula (A): Q 1 N = N Q 2 N = N Q (A) 1 3   wherein Q and Q each represents a substituted phenyl or naphthyl group having at least one SO 3 M substituent and Q 2 represents a substituted naphthyl group having at least one SO 3 M substituent, M being a selected base between   cations such as Na, K, Li, NH 4 and an amine salt.   2 Recording liquid according to claim   cation 1, wherein the dye represented by the general formula (A) is present in an amount of 0.1 to 20% by   weight based on the weight of the recording liquid.   A recording liquid comprising a coloring material which is an imaging component and a liquid medium for dissolving or dispersing the coloring material, characterized in that it contains as an imaging component at least one of one of the dyes represented by the following general formula (B): OH o 3 Sy N = N N = N NHR (B) MO 3 S SO 3 M SO 3 M   in which R is a representative of the group comprising the residues -COCH R 3 6 _COCH 3 ' CO R 9 R 1 R 2 1 R-1 R 4 I-R 5 R R 9 OH _So 2, and N N R 7 R   R 8 -ce R 1, R 2, R 3 R 4 R 5 R 6 R 7 R 8 and R 9 each being a representative of the group comprising H, CH 3, C 2 H 5, Cl, NH 2, OH and OCH 3; and M represents a chosen base between   cations such as Na, K, Li, NH 4 and an amine salt.   A recording liquid according to claim 3, characterized in that the dye represented by the general formula (B) is present in an amount of from 0.1 to 20% by weight based on the total weight of the recording liquid.